Image production utilizing multifunctional light sensitive compounds

Abstract

A layer of a liquid composition containing (A) a heat-activated latent polymerizing agent for 1,2-epoxides with (B) a light-sensitive compound having in the same molecule at least one 1,2-epoxide group and at least one chalcone or cinnamate group, or with a mixture of (C) a compound containing at least one 1,2-epoxide group together with (D) a compound containing at least one chalcone or cinnamate group, is heated so that the layer solidifies due to thermal polymerization through the 1,2-epoxide group, remaining, however, photocrosslinkable. The solidified layer is exposed in a predetermined pattern to actinic radiation, the parts so exposed becoming photocrosslinked through the chalcone or cinnamate unit(s) and hence insoluble. An image is produced which can be developed by means of suitable solvents. An example of a suitable latent polymerizing agent (A) is boron trichloride-N-methylpiperidine complex, and a suitable light-sensitive compound (B) is 1-(p-(glycidyloxy)phenyl)-5-phenylpenta-1,4-dien-3-one.

What is claimed is: 
     
       1. A process for the production of an image which comprises (i) heating a layer, supported on a carrier, of a liquid composition containing   (A) a heat-activated latent polymerizing agent for 1,2-epoxides with   (B) a light-sensitive compound having in the same molecule at least one 1,2-epoxide group of formula ##STR9##  and at least one chalcone or cinnamate group of formula   --Ar--x--                                                  II        wherein Ar is a benzene ring or a benzene ring substituted by alkyl, cycloalkyl, alkenyl, alkoxy, alkoxycarbonyl, each of these groups having a maximum of nine carbon atoms, halogen, hydroxy, a primary, secondary or tertiary amino, nitro, a carboxyl, sulfonic or phosphonic acid group or salt thereof;   X is a chain of the formula ##STR10## R 1  and R 2  individually denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or conjointly denote a polymethylene chain of 2 to 4 methylene groups,   R 3  and R 4  each denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a phenyl group, and   a and b each denote zero, 1, or 2 with the proviso that they do not both denote zero,   or with a mixture of   (C) a compound containing at least one 1,2-epoxide group of formula I, together with   (D) a compound containing at least one chalcone or cinnamate group of formula II,   or with a mixture of a light sensitive compound (B) with a compound (C) and/or (D) as herein defined,   such that the layer solidifies by thermal polymerization and becomes essentially non-tacky but remains photocrosslinkable, and subsequently,   (ii) exposing the solidified layer to actinic radiation in a predetermined pattern such that exposed parts of the layer are crosslinked and   (iii) removing those parts of the layer which have not become substantially crosslinked by treatment with a solvent therefor.   
     
     
       2. A process according to claim 1, in which the group of formula I forms part of a 2,3-epoxypropyl group. 
     
     
       3. A process according to claim 2, in which the 2,3-epoxypropyl group is directly attached to an atom of oxygen, nitrogen, or sulphur. 
     
     
       4. A process according to claim 1, in which the group --Ar--X-- is a cinnamoyloxy group or forms part of a group of formula ##STR11## where X 1  denotes a group of formula III, IV or V, each R 5  represents a halogen atom, an alkyl, cycloalkyl, alkenyl, alkoxy, or alkoxycarbonyl group containing up to 9 carbon atoms, a hydroxy group, a primary, secondary or tertiary amino group, a nitro group, a carboxyl, sulfonic, or phosphonic acid group or a salt thereof,   each c represents zero or an integer of 1 to 4,   R 6  denotes an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms or an alkaryl or aralkyl group of 7 to 10 carbon atoms, or each of said groups being substituted by one or more hydroxyl groups, and   R 7  denotes an alkylene group of 1 to 6 carbon atoms, an alkenylene group of 2 to 6 carbon atoms, a cycloalkylene group of 3 to 6 carbon atoms, an arylene group of 6 to 15 carbon atoms, or an alkarylene or aralkylene group of 7 to 10 carbon atoms.   
     
     
       5. A process according to claim 4, in which R 6  denotes a group of formula ##STR12## or a methyl or ethyl group, in which R 5  and c are as defined in claim 4. 
     
     
       6. A process according to claim 4 in which R 7  denotes a group of formula ##STR13## in which R 5  and c are as defined in claim 4. 
     
     
       7. A process according to claim 4, in which (B) is a glycidyl ester of a cinnamic acid, a partial ester formed by reaction of an epoxide resin with less than one equivalent of a cinnamic acid, a glycidyl ether of a monohydric or dihydric phenol containing a chalcone unit, a glycidyl ether prepared by reacting a diglycidyl ether containing a chalcone unit with a bisphenol or with a hydantoin, or a glycidyl derivative prepared by reacting a diglycidyl derivative of a bisphenol or hydantoin with a hydroxyl-substituted chalcone. 
     
     
       8. A process according to claim 4 in which (B) is a glycidyl ether of formula ##STR14## where R 8  denotes a methyl or ethyl group, and X 1 , R 5  and c are as defined in claim 4.   
     
     
       9. A process according to claim 7 in which (B) is glycidyl cinnamate or a partial reaction product of cinnamic acid with an epoxidised novolak or a diglycidyl ether of bisphenol A. 
     
     
       10. A process according to claim 1 in which (B) is a compound of formula ##STR15## where R 8  denotes a methyl or ethyl group, and R 9  represents a hydrogen atom or a hydroxy group.   
     
     
       11. A process according to claim 7 in which (B) represents a glycidyl ether prepared by reaction of a bisphenol A diglycidyl ether with 2,4-, 2',4-, 2',4'-, 2',3-, 2,5'-, 2,2'-, 4,4'-, or 3,4'-dihydroxychalcone, or 1,5-bis(p-hydroxyphenyl)penta-1,4-dien-3-one, a glycidyl derivative prepared by reacting N,N'-diglycidyl-5,5-dimethyl hydantoin with 1,5-bis(p-hydroxyphenyl)penta-1,4-dien-b 3-one, 4,4'-diglycidyloxychalcone, 1,4-bis(3-(4-glycidyloxyphenyl)-3-oxo-1-propenyl)benzene, 4,4'-diglycidyl-2,6-dimethylchalcone, 1-(p-glycidyloxyphenyl)hexa-1,4-dien-3-one, 1-(p-glycidyloxyphenyl)-5-phenylpenta-1,4-dien-3-one, 1-(p-glycidyloxyphenyl)-5-(p-hydroxyphenyl)penta-1,4-dien-3-one, or 1,5-bis(p-glycidyloxyphenyl)penta-1,4-dien-3-one. 
     
     
       12. A process according to claim 1, in which the compound (C) is a mono or polyglycidyl ester, a mono- or polyglycidyl ether, or a poly(N-glycidyl) compound. 
     
     
       13. A process according to claim 12 in which the compound (C) is 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, a diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane or butane-1,4-diol, or 1,3-diglycidyl-5,5-dimethylhydantoin. 
     
     
       14. A process according to claim 1, in which compound (D) is a full or partial ester of cinnamic acid with an aliphatic glycol or a polyol, or an epoxide resin that has been fully esterified by a cinnamic acid. 
     
     
       15. A process according to claim 4, in which (i) the compound (D) is of formula ##STR16##  where X 1 , R 5  and c are as defined in claim 4, and   Y denotes an oxygen or sulphur atom, or   (ii) the compound (D) is an epoxide resin that has been advanced to negligible epoxide content by reaction with a chalcone of formula XVII or XVIII in which one or two groups R 5  are hydroxy, carboxyl, or primary and secondary amino groups.   
     
     
       16. A process according to claim 1, in which (A) has a significant heat-polymerising effect on (B) and (C) only at temperatures above 100° C. 
     
     
       17. A process according to claim 16, in which (A) is a complex of boron trichloride or of boron trifluoride, a chelate of boron difluoride, dicyandiamide, or an imidazole. 
     
     
       18. A process according to claim 17, in which (A) is a complex of boron trichloride with a tertiary amine or of boron trifluoride with a triaryl phosphine, with piperidine or with a primary amine. 
     
     
       19. A process according to claim 1, in which the said layer is heated at a temperature of 120° to 200° C. for from 2 to 20 minutes.